Plastics



Patented Sept. 3, 1946 e 2,407,131

TED STATES PATENT OFFICE PLASTICS Herman A. Bruson and George B.-.Butler,. Philadelphia, Pa., assignors to Rohm & Haas Company, Philadelphia, Pa., a. corporation o Dela- This invention relates to explosive or readily 26 grams (0.10 mol) of 2,4,6-trinitrophenylethcombustible plastics and deals more particularly anol added irrsolid form. Stirring was-continued with trinitrophenylethyl esterst of. acrylic or ofand the reaction mixture heated gradually to methacrylic acidand polymers. thereof. I reflux and refluxed for one-half hour. After the It is already known that traces of polynitro- 5 mixture had been cooled, the solution was washed aromatic compounds, such as trinitrobenzene or thoroughly with NazCO'a and water, and the trinitrotoluene, will inhibit or entirely suppress benzene was removed under vacuum on a steam the polymerization of acrylic or methacrylic bath. The residue was a resinous material, but, esters, for example, methyl acrylate or methyl after: washing with. dilute potassium hydroxide methacrylate. It' was surprising to discover, 10' solution, it became a crystalline" solid. It was therefore, thatthe trirritro'phenyletliylesters of recrystallized from methanol and melts, when acrylic or methacrylic acid polymerize readily to pure, at 70 C. On heating at 100 C. with 1-5% hard, tough plastics when these esters are heated of benzoyl peroxide, it polymerized to a hard, with organic polymerization catalysts such as brown resin which melts at 80-90' C. peroxides, for example, benzoyl peroxide. The

nitroplastics thus obtained are useful for the Example 2 preparation of military explosives. 2;4,6-txinitrophenylethyl methccrylate.-(A) In carrying out this invention, it has been found To 10.4 grams (0.04 mol) of 2,4;6-trinitrophenyh advantageous to prepare the monomeric esters ethanol was added 9.2 grams (0.06 mol) of methy esterifying t 0D ylethanol with acrylic anhydride, and. the reaction mixture was the acid chloride or anhydride of acrylic or methheated for one hour in an oil bath at l10-120 C.

y c a d respectively e 2,4,6-trinitro- After the mixture had been cooled, the resinous phenylethanol used is obtained by condensing product was washed with .1 N sodium hydroxide TNT (trinitrotoluene) with formaldehyde. The solution to remove the excess anhydride and the monomeric esters obtained are crystalline solids acid formed in the reaction. After a thorough having the general formula: washing with cold water, the product became solid. It was recrystallized from ethanol. The I pure ester melts at 94 C. Analysis: Found: C=44.3%; H=3.60%; N=

13.05%. Calculated for C12H11O8N3: C=44.3.%; H= 3,39%; N=12.9%. fi g fgggf fi g ifi the gmup cmsstmg On heating the ester at 110 120" 0. with 2-5% The polymerization of these esters can be car- M g g g gi fi 1t polymenzes w brown ried out at a temperature at which they are fluid, i. e., at or somewhat above their melting points, (B) grams 9 of lg g preferably at 95120 C., or in solution, as, for phenylethantl was dlsso Ved.m S of W enexample, in acetone at the boiling point thereof. Zene by heatmg and p q of grams (0'02 The peroxides which can be used include benzoyl, mol) of methacrylyl 9 m 20 0020f dry p lauroyl or other organic peroxide The polymer to zene was added dropwise to the refluxing 80111131011. ization can also be carried out in aqueous suspen- R'tafiuxmg was confirmed for Afterfihe sion emulsion in which case ammonium m xture had been cooled, the so ut1on was was ed sulfate can be used as polymerization catalyst. iqueous a sglutlora g Witter the The following examples illustrate this invenso Ven remove un er re use p esstlre n tion: 1 4a steam bath. The product was recrystallized from Example 1 ethanol and it melts at 94 C. It polymerizes in the same way as the product prepared by the 2,4,6-trinitrophenylethyl acrylate.To a viganhydride method described above. orously stirred suspension of 21 grams (0.1 mol) These resins burn with considerable vigor.

of phosphorus pentachloride in 50 cc. of dry ben- 50 When a flame is applied, they become fluid bezene was added 14.5 grams (0.2 mol) of acry ic fore igniting, but, after ignition, they burn conacid from a dropping funnel While the temperatinuously, leaving only a small carbonaceous resture was kept below 10 C. The reaction mixture idue. They are soluble in ketones' but are inwas then heated in a Water bath at 30'-35 C. for soluble in alcohols, hydrocarbons, and chlorinated one-half hour. It was then cooled to 20 C. and solvents. They are partcularly valuable as bind- N02 R O wherein R is a member of the group consisting of hydrogen and methyl. V

2. As a new compound, a substance having in its monomeric form the formula:

CH:=CHOO 0-CH1CH N01 3. As a new compound, a substance having in its monomeric form the formula:

4. A polymer of an ester having in its monomeric form the formula:

wherein R is a member of the group consisting of hydrogen and methyl.

5. A polymer of an ester having in its monomeric form the formula:

6. A polymer of an ester having in its monomeric form the formula:

N02 CH:

7. As a new compound, the ester:

wherein R. is a member of the group consisting of hydrogen and methyl.

8. As a new compound, the ester:

9. As a new compound, the ester:

I 011,:(1-00 o CHaCH No,

HERMAN A. BRUSON. GEORGE E. BUTLER. 

